中文摘要
通过设计、合成模拟细胞色素 P-450 氧化酶氧化机理的仿生催化氧化的金属Salen 催化剂,筛选出高选择性地催化烯烃环氧化的高效催化剂。.研究金属 Salen 配合物的可调结构参数对催化氧化反应活性、选择性的影响,期望选择性地调控反应,获得所需的产物。采用环境友好的超临界二氧化碳和聚乙二醇组成的两相溶剂体系,通过聚乙二醇固定均相催化剂或使用所设计的金属Salen 功能化的聚乙二醇作为催化剂,超临界二氧化碳萃取分离产物,或采用PEG 不良溶剂使功能化的PEG 沉淀,以达到均相催化剂与产物的分离和循环使用。这种"均相反应、异相分离"策略,可望实现均相催化反应、分离一体化,即均相催化反应过程的连续化。.基于二氧化碳与催化剂的弱相互作用以及催化活化原理,单组分双功能或双组分双功能的高效催化剂用于各类噁唑啉酮和碳酸酯的合成。通过采用环境友好的反应介质(如超临界二氧化碳、聚乙二醇和离子液体等)及催化剂的设计、分离和循环利用策略,建立具有重要工业应用背景的羧酸酯、噁唑啉酮和碳酸酯合成新方法以及环境友好的新工艺。
英文摘要
Transition metal salen complexes have been successfully used as models for the cytochrome P-450 enzyme, with respect to the oxidation of organic compounds. We design and plan to synthesize Metal-salen complexes as the mimic P-450 catalysts for oxidation of aromatic substrates and epoxidation of olefins.. Efforts to convert CO2 to useful chemicals will inevitably rely on its activation via either metal coordination or weak interaction between active species and CO2 molecule. Metal-CO2 complexes may provide both structural and functional models for surface-bound intermediates in catalytic conversion processes. Development of catalytic methods for chemical transformation of CO2 into useful compounds is of paramount importance from a standpoint of C1 chemistry and so-called green chemistry and sustainable society. .The catalyt performance and selectivity of products could be tuned and controlled by their molecular structure of the metal-salen complexes. The highly active catalysts are expected to find through systematical screening the metal-salen complexes..The biphasic catalysis systems using supercritical carbon dioxide (scCO2) as thecontinuous phase and another green reaction medium, such as polyethylene glycol as the stationary catalyst phase are devised for the metal-mediated chemical reactions. An important advantage of adopting scCO2 with those biphasic systems from an engineering point of view was the possibility to combine reaction and separation into only one integrated process, namely the so-called homogeneously reacted while heterogeneously separated process..A concept and device originating from free-radical chemistry of PEG thermal degradation in conjunction with compressed CO2 would herein be introduced, whereby PEG radical assumed to be generated from PEG thermal oxidative degradation to successfully initiate a broad spectrum of free radical reactions in a practically utilizable manner with cost-efficient and environmentally friendly benefits, in which PEG/O2/CO2 acts as initiator, oxidant and solvent.
结题摘要
通过设计、合成模拟细胞色素 P-450 氧化酶氧化机理的仿生催化氧化的金属Salen 催化剂,筛选出高选择性地催化烯烃环氧化的高效催化剂。研究金属 Salen 配合物的可调结构参数对催化氧化反应活性、选择性的影响,期望选择性地调控反应,获得所需的产物。采用环境友好的超临界二氧化碳和聚乙二醇组成的两相溶剂体系,通过聚乙二醇固定均相催化剂或使用所设计的金属Salen 功能化的聚乙二醇作为催化剂,超临界二氧化碳萃取分离产物,或采用PEG 不良溶剂使功能化的PEG 沉淀,以达到均相催化剂与产物的分离和循环使用。这种"均相反应、异相分离"策略,可望实现均相催化反应、分离一体化,即均相催化反应过程的连续化。基于二氧化碳与催化剂的弱相互作用以及催化活化原理,单组分双功能或双组分双功能的高效催化剂用于各类噁唑啉酮和碳酸酯的合成。通过采用环境友好的反应介质(如超临界二氧化碳、聚乙二醇和离子液体等)及催化剂的设计、分离和循环利用策略,建立具有重要工业应用背景的羧酸酯、噁唑啉酮和碳酸酯合成新方法以及环境友好的新工艺。
